Method of making ester salts



m ma m. a, 1944 UNITED STATES PATENT OFFICE I lHETHOD F lizizilfzflls'l'lilt SaLTS Joseph Hilly James,

Pittsburgh, Pa., assignor to Clarence P. Byrnes, Pittsburgh, Pa., trustee No Drawing. Application June 24, 1939, f

Serial No. 280,97

11 Claims. (01. 260-453) My invention relates to ester salts of polybasic acids and is designed to provide a simple, cheap, and efflcient process for their production from straight aliphatic hydrocarbons'such as petroleum fractions.

In my well known process for. vapor phase partial oxidation of petroleum fractions, this step cracks some of the aliphatic chains and produces lighter bodies of less molecular weights, and also a variety of oxygen derivatives is formed such as alcohols, aldehydes, oxygenated acids, etc., in different molecular weights.

In my present process I use as raw material, a heavy petroleum fraction in the range of gas, oil, or other fraction boiling above 260 C. to 280 or 300 C. Since it is desirable to obtain a-mixture of the heavier alcohol above Ca and preferably above C12, I have found that I can greatly improve my production of such alcohols by fractionating the partial oxidation mixture and cutting out the lower fraction containing bodies below Ca treated with a polybasic acid, usually sulfuric acid, in the usual way, producing alkyl acid sulfates. These are preferably neutralized at once by a suitable alkali or alkaline carbonate, thus giving the desired ester salts.

The advantages of my invention result from the improved product, the use 01' cheap raw material, and the simplicity of the steps used.

The fractionating may be carried out in other ways and may be used after the hydrogenation, though I prefer to use it prior thereto; and other changes may be made without departing from my invention.

1. The method consisting of partially oxidizing aliphatic hydrocarbons into oxygen derivatives or C12, and also hydrogenating, before treating with a polybasic acid such as sulphuric acid,

phosphoric acid, arsenious acid or equivalent. 7

The fractionating is preferably carried out by distilling the condensed oily partial oxidation product prior to hydrogenation since thisavoids hydrogenating the lighter portions which are below C8 or C12, but may be carried out after hydrogenation. In fractionating prior to hydrogenation, I preferably distil over the lighter portion up to about 200 C. (with or without vacuum) and then after reaching the next heavier portion employ vacuum distillation since this purifies the desired portion from Cs or C12 up to about C20, leaving behind the heavy still residue containing impurities. Y

The hydrogenation which is preferably carried out under superatmospheric pressure with a suitable catalyst, and which may be in accordance with my United States Patent 1,681,238 of August 21, 1928, may be controlled to reduce substantially all the bodies in the partial oxidation product to alcohols. This avoids complications due to the presence of other bodies than alcohols and improves the odor and color.

I have found that in order to get a sulfation stock of good color and odor, the vacuum distilla tion prior to hydrogenation greatly helps the hydrogenation step in attaining the desired color of hydrocarbons in the range from alcohols to organic acids containing oxygen derivatives in the range from alcohols to acids including derivatives other than alcohols and acids, fractionating and hydrogenating the partially oxidized product and treating a portion of the product in a range above Co with an inorganic polybasic acid.

2. The method consisting of, partially oxidizing mineral oil into oxygen derivatives of hydrocarbons in the range from alcohols to organic acids containing oxygen derivatives in the range from alcohols to acids including derivatives other than alcohols and acids, fraction-ating and thereafter hydrogenating a portion of the partially oxidized product and treating a portion of the hydrogenated product in a range above Cc with an inorganic polybasic acid.

3. The method consisting of partially oxidizing mineral oil into dinerent oxygen derivatives of hydrocarbons in the range from alcohols to organic acids including oxygen derivatives other than alcohols and acids, fractionating the product into different fractions containing similar bodies of different average molecular weights, by

drogenating a fraction extending from about Ca and odor, especially since otherwise the hydrogenation of that part of the stock containing the residue would uselessly add to the expense.

Following hydrogenatiomthe mixture of heavy alcohols from Ca or C1: u to about C20 may be I upward and treating the resulting mixture of alcohols above about Ca with an inorganic polybasic acid.

4. The method consisting of partially oxidizing mineral oil into different oxygen derivatives of hydrocarbons in the range from alcohols to organic acids including oxygen derivatives other than alcohols and acids, fractionating the product into diflferent fractions containing similar bodies of different average molecular weights, hy-

, drogenatin-g a fraction extending from about Cs upward and treating the resulting mixture of alcohols above about'Ca with an inorganic poly material.

5. The method consisting partial oxidation product of mineral oil containing oxygen derivatives of diflerent classes in the range from alcohols to organic acids including oxygen derivatives other than alcohols and acids into fractions of different boiling ranges, hydrogenating an intermediate fraction containing alcohols from about Cs upwards and then treating the hydrogenated product with an inorganic polybasic acid. I

6. The method of treating a partial oxidation product containing alcohols and other oxygen derivatives oi aliphatic hydrocarbons, consisting in distilling off, purifying, and separating a fraction of intermediate average molecular weight from the heavier portion thereof, and then hydrogenating said purified intermediate distillate and treating it with an inorganic polybasic acid.

'7. The method of treating a partial oxidation product containing alcohols and other oxygen derivatives of aliphatic hydrocarbons, consisting in vacuum-distilling oil, and separating a fraction of intermediate average molecular weight from the heavier portion thereof, and then hydrogenating said purified intermediate distillate and treating it with an inorganic polybasic acid.

8. 'I'he'method oi'treating a partial oxidation product containing alcohols and other oxygen derivatives of aliphatic hydrocarbons consisting in removing a lighter portion, distilling over, purifying, and separating a portion of intermediate average molecular weight, leaving a heavier portion as still residue,- and then hydrogenating \oi fractionating a g the intermediate purified traction and treating it with an inorganic polybasic acid.

9. The method of treating a partial oxidation product containing alcohols and other oxygen derivatives of aliphatic hydrocarbons, consisting in distilling off a plurality of fractions to purifyand separate them from a heavier portion of the product and then hydrogenating anintermediate purified fraction extending from about Cs upwards and treating the hydrogenated fraction with an inorganic polybasic acid.

10. The method of treating a vapor phase partial oxidation product of mineral 011 containing oxygen derivatives of aliphatic hydrocarbons in the range from alcohols to organic acids including oxygen derivatives other than alcohols and acids consisting of fractionating the product, vacuum distilling and purifying a heavier fraction and separating a lighter portion of the heavier fraction, and then hydrogenating said purified lighter portion and treating it with an inorganic polybasic acid.

11. The method of treating a vapor phase partial oxidation product of mineral oil containing oxygen derivatives of aliphatic hydrocarbons in the range from alcohols to organic acids including oxygen derivatives other than alcohols and acids and including saponiflable compounds, consisting of fractionating the product, vacuum distilling and purifying a heavier fraction and separating a lighter portion of the heavier fraction, and then hydrogenating said purified lighter portion and treating it with an inorganic polybasic acid.

JOSEPH HIDY JAMES. 

